Condensation products of a fluoroacetone and phenols having a bridged phenyl group



CONDENSATION PRonUcTs OF A FLUOROACE- TONE AND PHENOLS HAVING A BRIDGEDPHENYL GROUP V United States Patent Ofitice 3,281,465 Patented Oct. 25,1966 s represents one of the digits 0, l and 2, and t represents one ofthe digits and 1.

From the foregoing, it will be noted that the fluoroacetone reactingmust contain one, two or three fluorine H b t st k 1 B i l w H H K NJ, 5atoms per primaiy carbon atom, the other substituents N0 Drawing. FiledNov. 15, 1963, Ser. No. 323,911 being hydrogen, or another halogen, suchas bro e, 6 Claims. (Cl. 260--559) chlorine, and/or iodine. The otherreactant must be a phenol, connected through a bridge, to anunsubstitued or Th1$ lIlVeHtlOIl relates to novel and hlghly usefulc011- substituted phenyl group, which may contain halogens as densationproducts of a fluoroacetoneand a phenol hav- 10 substituents, as 11 as ah li group 5 a bl'ldged p y P- M0re p y, It deals A typical reaction,according to this invention is as with a reaction product of afluoroacetone containing two f ll to siX fluorine atoms and a phenol,alone or substituted, H connected by a bridge to a phenyl group, whichmay be o H free or substituted. 15 g l The reaction involved here may beoutlined generally (CFCMOO as follows: 2 Br 0 4-BromosalicylanilideDichlorotetrafluoroacetone 2 R 011 X n (oX Frnoo i E) (I) O-N Yt 0H Br ROlFCC-OF2O1 X, Xn

Br I Y F,X,,G-GQX,,F, CN

l s H 11 11 2,2-Dichlorotetrafluoropropylene bis R(4-bromosalicylanilide)fl These compounds may be prepared in accordancewith H the following procedure: wherein:2,2'-dichlorotetrafluoropropylene bis (4'-br0mosalicyl- R is a bridgingradical of the class consisting of 40 amllde) O H About 22 moles ofdichlorotetrafiuoroacetone are added II H to a mixture of 1.0 mole of4'-bromosalicylanilide and 15 O N and C moles of anhydrous hydrogenfluoride in a copper am- X is a substituent of the class consisting ofhydrogen, poule, cooled with Dry Ice. After sealing the ampoule,chlorine, bromine and iodine, it is heated for 10 hours in a steam bath,after which the Y is a substituent of the class consisting of hydrogenand contents are poured into a copper vessel. The hydrogen OH, fluorideis evaporated and the residue is crystallized from n represents one ofthe digits 0, l, 2, and 3, ethylene chloride 'to separate the productfrom unreacted p represents one of the digits 0, 1 and 2,when p plus rbromosalicylanilide. Yields average about 70-80% of equal 3, theory. rrepresents one of the digits 1, 2, and 3, when 2 plus Table I listsexamples of compound prepared in accord-- equal 3, ance with the presentinvention:

TABLE I Analysis for Halogen Percent Calculated (percent) No. CompoundFormula F 01 Br F Cl Br ii i C-N 1 CF3- GF: CzgHrgOqNzFgBlz "H A H TABLEI.Cont1nued Analysis for Halogen Percent Calculated (percent) No.Compound Formula F Cl Br F Cl Br OH OH I I mg onfi 1 7 0113-0-01,CmHlgOJqCl;

| (M.W. 686) 16. 7 20. 6 16. 6 20. 7 Cll lCHyl :LCI

H OH

OH OH I I CIT ICH T I01 8 ClFgC-C-CF2C1 Cz9H13O F C1n (M.W. 719) 10. 629. 7 10. 6 29. 6 c1 cnr-ol H H JH (3H 01- c11,-@-01 9 ClqF O- I ()F C1:O29H1gO4F1Cl 5. 1 37. 9 5. 1 37. 8

(HQ GHQ 01 OH H (])H (1)11 10 F: C-C-CFa CI C29HuO4Fe 1n I I (M.W. 893)12. 5 39. 6 12. 8 39. 8

These compounds have been found to have excellent activity againstbacteria, and fungi, such as S. aureus and A. niger. Typical germicidaldata are given in Table II:

Minimum inhibitory concentration against S. aureus was determined asfollows: Ten milligrams of each compound were dissolved in 1000 ml. ofnutrient broth ad usted to pH 6.8. From each such dilution, 10 ml.dilutions were prepared in sterile broth varying in strength between 10ppm. and 0.2 p.p.m., utilizing 20 tubes for each compound Each dilutionwas inoculated with 0.1 ml. of a 24-hour old broth culture of S. aureus,and all tubes were read for density on a densitometer, and the valuesrecorded. A control broth was inoculated. All tubes were inoculated at37 C. for exactly 24 hours. Following inoculation, all tubes werere-read in the densitometer and, since growth of the organism createsturbidity, the higher the densitometer reading. the greater the growth.A turbidometric reading equal to that of the control would indicate noactivity of the compound. A reading equal to that prior to incubationindicates 100% activity of the compound. The above results show theconcentration at which increase in densitometer reading was observed.

In determining the activity of the compounds against A. niger, agarplates were used in place of nutrient broth tubes, as in the case oftesting antibacterial activity. The plates were prepared withconcentrations of the compounds ranging from 1 p.p.m. to 10 p.p.m.,utilizing 20 plates for each compound. The plates containing the lowestconcentration of compound which inhibited fungal growth for 14 days atroom temperature were considered as the end-point and, in cases wheregrowth was doubtful between one concentration and the next higher, thereading was assumed to fall between such concentrations.

These compounds have been found to be excellent mildew-proofing andgermicidal agents for fibrous materials such as cloth, leather, paper,wood, and the like. Treatment of fibrous material may be made with asolution or dispersion of the germicide in a liquid medium, leavingabout 0.001% to 0.05%, or even 0.5%, or as much as 5.0% by weight of thegermicide in the fibrous material.

The germicides of the present invention also may be incorporated inplastics, such as rubber, polyethylene, polystyrene, polyurethane,nylon, and similar plastoform and elastoform compositions byincorporating the germicide in an amount of 0.001% to 0.05% or even 0.1%or as much as 0.5% and 5.0% in the batch which is mixed or kneaded priorto vulcanization, extrusion or other forming operation.

The compounds of the present invention are particularly valuable indetergent and toilet detergent compositions, in the amount of 0.001% to0.01% by weight, and to about 0.5% or even 1.0%, 2%, or even They may beadmixed in commercial toilet soaps, such as neutral high grade sodiumand potassium salts of fatty acids from tallow, olive oil, palm oil, andthe like, above or with non-soap synthetic detergents, e.g., non-ionic,anionic, or cationic.

The term detergent employed herein includes fatty acid soaps, as well assynthetic detergents, and other detergents, such as fatty alcoholsulfates, fatty acid amides, sodium tripolyphosphates, and combinationsthereof. The term toilet soap used herein also is employed in itspopular meaning, that is, those compositions employed for cleansing theskin and prepared from an alkali metal compound, such as potassium orsodium hydroxide and fat or fatty acid, both saturated and unsaturated.The compositions described herein also include other antiseptic agents,emollients, Water softeners, antioxidants, dyes, perfume, cold creamadditives, and the like.

The germicidal compounds of the present invention may be used withanionic detergents, such as sodium hexadecyl sulfate, or with cat-ionicdetergents, as exemplified by dimethyl-stearamidopropyl-2-hydroxyethylammonium dihydrogen phosphate, or with non-ionicdetergents, such aspolyoxypropylene, polyoxyethylene condensates, alone or in admixturewith other detergents heretofore enumerated. They are also effective inscouring powders, detergent cleaners, and the like.

I claim:

1. A compound having the following generic formula:

I YA

R is a bridging radical of the class consisting of where:

O-N H I O H OH OH OH O CH WALTER A. MODANCE, Primary Examiner.

NATALIE TROUSOF, Assistant Examiner.

1. A COMPOUND HAVING THE FOLLOWING GENERIC FORMULA